Improved Electrocatalytic Water Splitting Reaction on CeO₂(111) by Strain Engineering: A DFT+U Study

Abstract

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Facet-Dependent Stability of Near-Surface Oxygen Vacancies and Excess Charge Localization at CeO2 Surfaces

“…From the calculations performed in this work for the higher vacancy concentration, we learn that the higher stability of surface vacancies at the (110) facet compared to subsurface ones, is about 2.6 times larger than previously predicted [63], and that the stability trend of subsurface vacancies is: (100) < (111) < (110), and therefore the one recently reported [57,63] is not correct.…”

“…With regard to theoretical studies on the reduced (111) facet, the computational methodology varies, but there is general consensus that subsurface vacancies are more stable than surface ones and, for some time now, that the Ce 3+ ions are preferably located in the outermost cationic plane in sites not adjacent to the vacancies, as much as possible [43-45, 49, 51-54, 56, 63, 65], in full accord with experimental results [33,37,38]. Therefore, the recent result by Wu et al [57] which reports that Ce 3+ are first neighbors to both surface and subsurface vacancies, is striking.…”

“…Table 3) [43,49,53]. Therefore, it is noticeable that Wu et al [57] missed to provide any calculated defect formation energy for V 2,2 A/B configurations using a (22) unit cell, but reported a V , A/B configurations with both Ce 3+ the first cationic coordination shell.…”

Facet-Dependent Stability of Near-Surface Oxygen Vacancies and Excess Charge Localization at CeO2 Surfaces

“…Table 3) [43,49,53]. Therefore, it is noticeable that Wu et al [57] missed to provide any calculated defect formation energy for V 2,2 A/B configurations using a (22) unit cell, but reported a V , A/B configurations with both Ce 3+ in the first cationic coordination shell.…”

Crystal facet and surface defect engineered low dimensional CeO2(0D, 1D, 2D) based photocatalytic materials towards energy generation and pollution abatement

“…Then water dissociation into hydroxyl takes place and surface vacancy facile the water dissociation step. And finally hydroxyl decomposition occurs and liberates H 2 through an asymmetric process, which involves oxidation of Ce 3+ to Ce 4+[158][159][160]. Further, in case of excessive hydroxylated CeO 2 , water hydroxylation and liberation H 2 might involve a new intermediate i.e Ce-H.…”